CAS: Expanding Base Metal-Catalyzed MHAT Reactions

CAS：扩展贱金属催化的 MHAT 反应

• 批准号: 1955922
• 负责人: Ryan Shenvi
• 金额: $ 46.44万
• 依托单位: The Scripps Research Institute
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955922&HistoricalAwards=false
• 关键词: CAS; Expanding; Base; Metal; Catalyzed

With this award, the Chemical Catalysis Program of the Division of Chemistry is supporting the research of Professor Ryan Shenvi of The Scripps Research Institute. Professor Shenvi and his research team are developing inexpensive, earth-abundant, and stable metal catalysts to add hydrogen to carbon-carbon double bonds. This work is providing sustainable alternatives to precious metal-catalyzed processes that have traditionally been used for this purpose. The Shenvi research group is investigating, simplifying, and adapting these reactions for large-scale implementation. They are also developing tandem processes to form new carbon-nitrogen and carbon-carbon bonds after the initial addition of hydrogen. These studies are providing students in the laboratory with training in catalyst design, reaction development, and complex molecule synthesis. Professor Shenvi is also engaged in outreach activities introducing the scientific method to elementary school students and to undergraduate students involved in the Scripps Summer Undergraduate Research Fellowship Program.Professor Shenvi and his research group have recently developed metal-catalyzed hydrogen atom transfer (MHAT) catalysts that can be used in combination with base metal cross-coupling catalysts as a sustainable approach to hydroelementation. To advance the breadth of these studies, new applications of MHAT catalysis in hydroamination and hydrobenzylation processes are being explored. In addition, a new MHAT catalytic cycle is being developed based on inspiration from hydrogen evolution reaction catalysts where reductive turnover is used to eliminate the challenges associated with the delicate balance of oxidant and reductant required in established MHAT systems. These investigations are advancing new modes of catalysis based on readily available metals, particularly manganese, with the optimal choice of and balance of silane reducing agent and oxidant being examined so as to produce a process that is both economical and efficient. This methodology development has the potential for broad scientific impact by providing a viable Mn-catalyzed alternative to precious metal-catalyzed alkene hydroamination.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

有了这个奖项，化学系的化学催化计划支持斯克里普斯研究所的Ryan Shenvi教授的研究。Shenvi教授和他的研究团队正在开发廉价、地球资源丰富且稳定的金属催化剂，以将氢添加到碳碳双键上。这项工作为传统上用于此目的的贵金属催化工艺提供了可持续的替代品。Shenvi研究小组正在研究、简化和调整这些反应，以便于大规模实施。他们还在开发串联过程，以在最初加入氢后形成新的碳-氮键和碳-碳键。这些研究为实验室的学生提供了催化剂设计，反应开发和复杂分子合成方面的培训。Shenvi教授还参与了向小学生和参加Scripps夏季本科生研究奖学金计划的本科生介绍科学方法的外联活动。Shenvi教授和他的研究小组最近开发了金属催化氢原子转移（MHAT）催化剂，该催化剂可与贱金属交叉偶联催化剂结合使用，作为可持续的水元素化方法。为了推进这些研究的广度，正在探索MHAT催化在加氢胺化和加氢苄基化过程中的新应用。此外，基于析氢反应催化剂的灵感，正在开发一种新的MHAT催化循环，其中还原周转用于消除与已建立的MHAT系统中所需的氧化剂和还原剂的微妙平衡相关的挑战。这些研究正在推进基于容易获得的金属（特别是锰）的新的催化模式，并检查硅烷还原剂和氧化剂的最佳选择和平衡，以产生既经济又有效的方法。 通过提供一种可行的Mn催化替代贵金属催化烯烃加氢胺化的方法，该方法的开发具有广泛的科学影响潜力。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Catalytic hydrogen atom transfer to alkenes: a roadmap for metal hydrides and radicals.

• DOI: 10.1039/d0sc04112b
• 发表时间: 2020-12-14
• 期刊: Chemical science
• 影响因子: 8.4
• 作者: Shevick SL;Wilson CV;Kotesova S;Kim D;Holland PL;Shenvi RA
• 通讯作者: Shenvi RA

Cobalt-catalyzed alkene hydrogenation by reductive turnover.

• DOI: 10.1016/j.tetlet.2021.153047
• 发表时间: 2021-03
• 期刊: Tetrahedron letters
• 影响因子: 1.8
• 作者: Vincent van der Puyl;Ruairi O. McCourt;R. Shenvi